STUDIES  IN  THE  METALLURGY  OF  BERYLLIUM 


BY 


OTTO  ERSKINE  HUNTLEY 
A.  B.  Hope  College,  1918 


THESIS 


Submitted  in  Partial  Fulfillment  of  the  Requirements  for  the 


Degree  of 


MASTER  OF  ARTS 


IN  CHEMISTRY 


IN 


THE  GRADUATE  SCHOOL 


OF  THE 


UNIVERSITY  OF  ILLINOIS 


1921 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 

may  31 1 92_Jr 

I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 

SUPERVISION  BY QITQ-JSRSKINE  HUNTLEY 

ENTITLED  STUDIES  IH  THE  METALLURGY  Off  BERYLLIUM 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


Recommendation  concurred  in* 


Committee 

on 

Final  Examination* 


^Required  for  doctor’s  degree  but  not  for  master’s 


2> 

T--  .2, 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/studiesinmetalluOOhunt 


\^l\ 


sg 

TABLE  OF  CONTENTS 

~ Page 


INTRODUCTION 

'0 

I.  Object  1 

II.  Occurrence  1 

III.  Historical  3 

EXPERIMENTAL 

IV,  Crude  Material  5 

V,  Parsons’  Method  of  Extraction  5 

VI.  Preparation  of  Beryllium  Chloride  7 

VII,  Electrolysis  of  Beryllium  Chloride  7 

VIII,  Treatment  of  Beryllium- Amalgam  9 

CONCLUSION 

IX,  Summary  11 

X . B ibl io  graphy  1 3 


V 


ACKNOWLEDGEMENT 

The  writer  takes  this  opportunity  to 
thank  Professor  B.  S.  Hopkins,  who  suggested 
thi3  research,  and  directed  the  work,  for  the 
invaluable  suggestions,  advice,  aid  and 
encouragement.  Thanks  are  also  tendered  to 
Dr.  H.  C.  Kreniers  for  placing  apparatus  at  the 
writer’s  disposal,  and  for  several  valuable 
suggestions. 


. 


. 


. . . . 


INTRODUCTION 


- 1 - 

I.  OBJECT « 

The  object  of  this  investigation  was  to  study  the  metal- 
lurgy of  beryllium  with  a view  to  the  discovery  of  a method 
that  would  prove  successful  on  the  large  scale.  The  plan 
suggested  was  to  carry  out  the  investigations  on  a small 
scale  and  if  a successful  method  was  discovered,  to  try  it 
out  on  a large  scale . 

The  difficulty  which  is  encountered  in  the  extraction 
of  beryllium  from  beryl  has  kept  beryllium  in  the  category  of 
«rare«  elements  altho  beryllium  bearing  minerals  occur  exten- 
sively. When  a method  is  proposed  by  which  beryllium  can  be 

prepared  cheaply  an  adequate  supply  of  the  mineral  will  be 
(1,3) 

available  , 

Beryllium  possesses  properties  which  make  it  useful  for 
the  manufacture  of  special  electrical  and  other  scientific 
instruments  and  apparatus)  its  alloys  with  copper  are  known 
to  possess  sonorous  properties;  its  salts  are  useful  in  the 
synthetic  preparation  of  pure  gems. 

II.  OCCURRENCE. 

Beryllium  occurs  chiefly  as  the  silicate,  beryl, 
Be3Alg(Si02) 6,  which  contains  11-15$  BeO.  Emerald  and  aqua 

marine  are  of  this  formula.  Gadolinite,  FeBe2Y2Si2Q|0  or 
Be2F3(Y0) 2 (Si04) 2,  5-11$  BeO:  Leucophanite  NaBeFCa(Si03) 2 , 

10-13$  BeO;  chrysoberyl,  Be(A102)2,  19-30$  BeO;  euclase, 

Be (AlQH) S10 a . 17-16$  BeO:,  Bertrandite,  Be2(3e0H) 2Si207, 


- 2 - 


40  -43$>  BeO;  and  eudidymite,  HHaBeSl 30Q , 10-11$  BeO , are  other 

(2,3) 

important  minerals.  Many  other  minerals  contain  beryllium. 
Beryl  was  the  source  of  material  for  this  investigation. 


III.  HISTORICAL. 

In  1798,  L,  N.  Vauquelin  announced  the  discovery  of  a new 
earth,  »la  terre  du  Beril" . He  made  the  discovery  in  attempt- 
ing to  prove  the  identity  of  beryl  and  emerald,  previously 
reported  by  Hauy,  when  he  found  that  on  boiling  a solution  of 
a precipitate  previously  supposed  to  be  aluminium  hydroxide  in 

potassium  hydroxide,  that  a portion  of  the  precipitate  was 

(4) 

thrown  out  of  solution.  The  name  proposed  by  Vauquelin 

was  translated  into  the  German  as  "Beryllerde"  from  whence 

came  "Beryllium"  . The  editors  of  Annales  de  Chimie  suggested 

the  name  "glucine"  because  of  the  sweet  taste  of  the  fulfate, 

Hut  later  investigators  have  objected  to  the  name  because  of 

(5) 

the  similarity  to  "glycine,"  and  others  because  the  sweet- 
ness, is  not  peculiar  to  beryllium  compounds  alone,  but  is 

(6) 

possessed  by  the  yttrium  earths.  Following  the  discovery 

of  the  element,  Vauquelin  studied  and  reported  the  properties 

(7,8,9,10)  (12),  (11) 

of  3ome  of  its  compounds.  Berzelius,  Gay-Lussac, 

and  others  also  studied  the  known  beryllium  compounds,  and 

prepared  and  reported  others. 

(13) 

In  1826,  Wohler  obtained  metallic  beryllium  as  a dark 

gray  powder  by  reducing  sublimed  beryllium  chloride  with  potass- 

(14) 

ium  in  a platinum  crucible.  About  the  same  time  Bussy 


- 3 - 


prepared  impure  bervliium  by  the  same  method. 

(15) 

In  1842,  Awdejew  made  the  first  determinations  of  the 

atomic  weight  of  bervliium  that  have  anv  claim  to  accuracy. 

(16) 

Weeren  (1854)  published  an  extended  and  careful  research 

on  beryllium.  He  determined  the  atomic  weight  by  the  ratio 

Ee0:S03  in  bervliium  sulfate  which  he  had  carefully  purified. 

(1?) 

In  1855,  DeBray  prepared  metallic  beryllium  as  a white 

metal,  specific  gravity  2.1,  by  the  reduction  of  the  chloride 

with  sodium  in  a current  of  hydrogen.  He  describes  the  proper- 

(16) 

tie 3 of  the  metal  and  of  various  compounds.  Charles  A, Joy, 

published  an  extended  bibliography  of  beryllium  up  to  1863. 

He  also  published  results  on  various  methods  of  decomposing 

beryl  and  methods  of  separating  aluminium  and  bervliium. 

(19) 

Nilson  and  Petersson  prepared  beryllium  by  heating 

the  chloride  to  bright  redness  with  sodium  in  a sealed  crucible. 

(30  T 

Kruss  and  Moraht  reduced  potassium  beryllium  fluoride  with 

(21) 

sodium.  Warren  reports  that  he  obtained  beryllium  by 

electrolyzing  fused  beryllium  bromide.  This  has  since  been 

(3) 

declared  a mistake  by  Parsons  who  states  that  the  bromide  is 

(22) 

not  a conductor  of  electricity.  Borchers  electrolyzed 

(23) 

potassium  ammonium  beryllium  fluoride.  Lebeau  obtained 
beryllium  by  electrolyzing  sodium  beryllium  fluoride.  A 
nickle  crucible  served  as  the  cathode  and  a graphite  anode  was 
used.  It  ms  only  necessary  to  melt  the  mass  with  a Bunsen 


- 4 - 

burner  and  then  the  current  (6-7  amps,  35  volts)  was  sufficient 
to  keep  it  molten. 

This  is  a brief  resume  of  the  various  methods  used  up  to 
this  time  to  prepare  metallic  beryllium. 


■ 

. 


l 


EXPERIMENTAL 


' 


r 


- 5 - 

IV.  the  crude  material. 


The  material  used  was  beryl  which  is  the  only  mineral 
of  beryllium  which  contains  enough  beryllia  to  make  its 
extract  ion  p ract ical . It  is  beryllium  aluminium  silicate, 
Be3Al 2 (Si03)  6,  and  contains  11-15$  BeO  . As  impurities  it 
contains  iron,  calcium,  and  magnesium.  The  beryl  used  came 
in  lumps  ranging  in  color  from  white  to  green  with  brown 
and  blue  streaks.  It  was  prepared  by  crashing  first  with  a 
sledge  hammer,  then  thru  a Elake  jaw-crusher,  where  it  was 
reduced  to  l/l6  inch.  The  material  was  then  rotated  in  a 
ball  mill  for  several  days  until  it  passed  thru  a 100-mesh 
sieve . 

(24) 


Analysis . 


Composition  of 

Beryl  : 

BeO 

10.  $ 

A1 2O  3 

M 

CD 

• 

Si02 

65.5 $ 

F e 20  3 

1.7  io 

CaO,MgO  ,H20 

3.8  $ (by 

difference) 


100.  $ 

V.  PARSON'S  METHOD  OF  EXTRACTION . 

One  hundred  gram3  of  beryl  were  fused  with  an  equal 
weight  of  sodium  hydroxide  in  a nickel  crucible,  in  a Case 


\ 

* 

. 


- 6 - 

furnace.  The  fused  mass  ms  "broken  up  and  just  covered  with 
water.  Concentrated  sulfuric  acid  was  added  in  slight  excess. 
The  product  of  several  fusions  was  treated  in  this  my  and 
then  the  whole  mass  was  heated  until  fumes  of  sulfuric  acid 
were  given  off.  The  residue  now  had  the  appearance  of  fine 
white  powder.  This  residue  was  treated  with  hot  water  when 
the  sulfates  of  "beryllium,  aluminium,  iron  and  sodium  passed 
into  solution  and  were  separated  from  the  3ilica  by  filtration. 
The  mother  liquors  were  evaporated  until  the  alums  began  to 
crystallize  out,  allowed  to  stand,  and  filtered  from  the  alum. 
Most  of  the  aluminium  was  separated  in  this  way.  The  liquor 
from  the  alum  wa3  treated  with  nitric  acid  to  convert  all 
the  iron  present  to  the  ferric  condition,  neutralized  with 
ammonium  hydroxide,  and  sufficient  sodium  acid  carbonate  added, 
in  crystals,  to  saturate.  The  solution  was  warmed(50° C . ) and 
shaken  frequently  for  24  hours.  Most  of  the  beryllium  passed 
into  solution  almost  free  from  aluminium  and  iron.  Ey  re- 
dissolving and  treating  the  residue  after  filtration  practi- 
cally all  of  the  beryllium  wa3  obtained  in  the  bicarbonate 
solution.  Ammonium  sulfide  was  added  to  thi3  solution  to 
remove  any  iron  that  might  have  dissolved,  and  the  solution 
filtered.  The  solution  was  diluted  to  ten  times  its  volume 
and  3team  passed  thru  the  liquid  to  the  boil ing  point , which 
caused  the  beryllium  to  be  precipitated  as  a.  fine,  granular 


- 7 - 

basic  carbonate,  xBeC03,  yEe(OH)2.  This  is  obtained  quite 
(26) 

pure  by  filtering  and  washing.  The  yield  was  about  80% 
of  the  theoretical. 

/ r2  p cA 

VI.  PREPARATION  QP  BERYLLIUM  CHLORIDE  * * 

The  basic  carbonate  of  beryllium  as  prepared  above  was 
dissolved  in  hydrochloric  acid  and  evaporated  to  dryness. 

The  residud  was  taken  up  in  water  and  it  was  found  that  a few 
drops  of  concentrated  hydrochloric  acid  were  usually  necessary 

(5) 

to  bring  it  into  solution,  due  to  the  formation,  on  evaporation 

(25) 

of  basic  mixtures  of  various  degrees  of  hydration. 

VII.  ELECTROLYSIS  OF  BERYLLIUM  CHLORIDE. 

Several  types  of  cell  were  tried  but  the  cell  finally 
used  was  of  the  nature  of  the  accompanying  drawing.  The  first 
ceil  was  a 600cc.  beaker  equipped  with  a mercury  cathode  and 
a graphite  anode.  Connection  was  made  to  the  mercury  through 
a platinum  wire  sealed  in  a short  length  of  glass  tubing. 

Direct  currents  of  110  volts,  and  of  12  volts  were  tried. 

With  the  110  volt  circuit  a bank  of  12  lamps  and  a carbon 
rheostat  resistance  were  inserted  and  varying  resistances  were 
tried.  The  graphite  anode  continually  wore  awa2/  under  the  action 
of  the  chlorine  and  settled  on  the  amalgam  from  which  it  was 
separated  by  rolling  in  cloth.  The  crude  cell  did  not  give  very 
satisfactory  results  and  the  cell  as  finally  used  was  constructed 


*S*/u.t  < on  . 


-8- 


as  follows:-  The  bottom  of  a 300  cc. bottle  was  removed  and 
a rubber  stopper  substituted  thru  which  were  passed  two 
lengths  of  glass  tubing.  One  piece  of  tubing  ended  at  the 
surface  of  the  stopper  and  was  used  to  draw  off  the  amalgam 
and  to  introduce  fresh  mercury.  This  was  accomplished  by 
means  of  a Y connection  (see  figure N to  which  was  attached 
two  separatory  funnels, one  for  the  amalgam, the  other  for  the 
mercury.  The  other  piece  of  tubing  terminated  about  1/2  inch 
higher  and  was  used  to  remove  the  electrolzed  solution  and 
to  introduce  fresh  aqueous  beryllium  chloride.  The  process 
was  made  more  or  less  continuous, although  not  automatic, 
by  connecting  this  tube, likewise, to  two  separatory  funnels. 
Connection  was  made  to  the  mercury  cathode  by  means  of  a 
Piece  of  glass  tubing  in  which  was  sealed  a short  platinum 
wire . The  tubing  was  filled  with  mercury  to  connect  the 
wires  from  the  source  of  current.  The  anode  was  a platinum 
wire  similarly  constructed , and  distant  from  the  cathode 
about  3 centimeters. 

Experiments  proceeded  with  varying  resistances  on  both 
the  110  and  10  volt  circuit.  As  finally  tried  the  10  volt 
circuit  w as  used  wi th  a sufficient  resistance  to  cause  a currenl 
of  1-2  amperes  to  flow  thru  the  cell.  The  electrolysis  was 
not  at  all  dependable.  Concentration  and  resistance  seemed 
to  play  an  important  part.  At  first  the  amalgam  seemed  to 


- 9 - 

form  readily,  but  after  a tire  equilibrium  was  reached  and 

no  more  amalgam  formed.  At  other  times  the  beryllium  salt 

hydrolyzed  and  had  to  be  removed  and  converted  to  the  chloride. 

With  careful  efforts  to  have  the  conditions  the  same  the  most 

unexpected  reactions  occurred  and  had  to  be  overcome.  Both 

(3) 

aqueous  and  alcoholic  solutions  of  beryllium  chloride  were 
tried  in  an  effort  to  easily  obtain  the  amalgam  but  with 
very  little  difference  in  the  result.  The  electrolysis  is 
still  unsatisfactory  and  merits  continued  research. 

VIII,  TREATMENT  O7?  THE  BERYLLIUM  AMALGAM  • 

An  effort  was  made  to  obtain  metallic  beryllium  from 
the  amalgam.  The  first  plan  suggested  was  to  heat  the  amalgam 
in  a stream  of  nitrogen.  The  beryllium  amalgam  was  placed 
in  a combustion  tube  in  a furnace  and  the  tube  connected  with 
a vacuum  pump  and  a source  of  nitrogen.  The  nitrogen  was 
prepared  by  drawing  air  slowly  through  ammonium  hydroxide 
and  then  through  a combustion  tube  containing  copper  oxide 
to  decompose  the  ammonia  into  nitrogen  and  water,  then  thru 
another  combustion  tube  containing  copper  gauze  to  remove 
the  oxygen  from  the  air.  The  gas  was  then  drawn  thru  a long 
series  of  drying  towers  containing  concentrated  sulfuric 
acid;  stick  potassium  hydroxide;  and  phosphorus  pentoxide 
respectively. 


- 10  r 


The  product  obtained  was  yellow  to  gray  in  color  and 
was  probably  a mixture  of  the  oxide  and  occluded  mercury. 

A supposition  that  the  nitride  might  have  formed  seemed 
unlikely  since  the  material  did  not  decompose  in  boiling 
water,  but  dissolved  in  hydrochloric  acid. 

It  was  next  decided  to  try  to  obtain  beryllium  from  the 
amalgam  in  vacuum.  The  first  trials  were  unsuccessful 
because  the  vacuum  was  not  high  enough.  The  metal  oxidized 
and  the  product  was  white  beryllium  bxide. 

Other  attemps  were  made  using  a mercury  pump  by  which 
vacuum  of  0.001  mm.  of  mercury  could  be  obtained  and  a gray 
powder  was  the  result.  After  several  such  runs,  the  product 
which  contained  a little  mercury  was  dissolved  in  hydrochloric 
acid,  separated  from  the  mercury,  and  precipitated  as  the 
hydroxide  with  ammonium  hydroxide.  This  was  filtered,  washed, 
and  dissolved  in  potassium  hydroxide.  Upon  boiling  beryllium 
hydroxide  was  again  precipitated. 


CONCLUSION? 


7 11  > 


IX.  SUMMARY • 

Eery Ilium  basic  carbonate  was  obtained  from  beryl  by 
the  method  suggested  by  Parsons.  No  attempt  was  made  to 
get  large  yields  but  rather  to  obtain  purity  of  product. 

The  basic  carbonate  was  converted  to  the  chloride  and  the 
aqueous  solution  electrolyzed  with  a mercury  cathode.  This 
gave  a beryllium  amalgam.  The  amalgam  was  heated  in  vacuum 
to  obtain  metallic  beryllium. 

The  investigation  shows  that  beryllium  amalgam  may  be 
formed  by  electrolyzing  aqueous  beryllium  chloride.  Metallic 
beryllium  may  be  obtained  by  heating  the  amalgam  in  vacuum. 

A new  method  of  obtaining  metallic  beryllium  was 
discovered. 


* 


' ■ • 

' 

■ 

‘ ' :j  . * cf  l If  ] 


- 13 


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2.  Browning,  P.  E.  Introduction  to  the  Rarer  Elements. 

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